Many-Body Description of STM-Induced Fluorescence of Charged Molecules.

A scanning tunneling microscope is used to study the fluorescence of a model charged molecule (quinacridone) adsorbed on a sodium chloride (NaCl)-covered metallic sample. Fluorescence from the neutral and positively charged species is reported and imaged using hyperresolved fluorescence microscopy. A many-body model is established based on a detailed analysis of voltage, current, and spatial dependences of the fluorescence and electron transport features. This model reveals that quinacridone adopts a palette of charge states, transient or not, depending on the voltage used and the nature of the underlying substrate. This model has a universal character and clarifies the transport and fluorescence mechanisms of molecules adsorbed on thin insulators.

Tip-Induced and Electrical Control of the Photoluminescence Yield of Monolayer WS2.

The photoluminescence (PL) of monolayer tungsten disulfide (WS2) is locally and electrically controlled using the nonplasmonic tip and tunneling current of a scanning tunneling microscope (STM). The spatial and spectral distribution of the emitted light is determined using an optical microscope. When the STM tip is engaged, short-range PL quenching due to near-field electromagnetic effects is present, independent of the sign and value of the bias voltage applied to the tip-sample tunneling junction. In addition, a bias-voltage-dependent long-range PL quenching is measured when the sample is positively biased. We explain these observations by considering the native n-doping of monolayer WS2 and the charge carrier density gradients induced by electron tunneling in micrometer-scale areas around the tip position. The combination of wide-field PL microscopy and charge carrier injection using an STM opens up new ways to explore the interplay between excitons and charge carriers in two-dimensional semiconductors.

Scanning Tunneling Microscope-Induced Excitonic Luminescence of a Two-Dimensional Semiconductor.

The long sought-after goal of locally and spectroscopically probing the excitons of two-dimensional (2D) semiconductors is attained using a scanning tunneling microscope (STM). Excitonic luminescence from monolayer molybdenum diselenide (MoSe_{2}) on a transparent conducting substrate is electrically excited in the tunnel junction of an STM under ambient conditions. By comparing the results with photoluminescence measurements, the emission mechanism is identified as the radiative recombination of bright A excitons. STM-induced luminescence is observed at bias voltages as low as those that correspond to the energy of the optical band gap of MoSe_{2}. The proposed excitation mechanism is resonance energy transfer from the tunneling current to the excitons in the semiconductor, i.e., through virtual photon coupling. Additional mechanisms (e.g., charge injection) may come into play at bias voltages that are higher than the electronic band gap. Photon emission quantum efficiencies of up to 10^{-7} photons per electron are obtained, despite the lack of any participating plasmons. Our results demonstrate a new technique for investigating the excitonic and optoelectronic properties of 2D semiconductors and their heterostructures at the nanometer scale.